NO145680B - ETHYLENE HOMO AND COPOLYMERIZATION CATALYSTS CONTAINING CHROME, TITAN AND ANY FLUOR, AND PROCEDURES FOR PREPARING THEREOF. - Google Patents
ETHYLENE HOMO AND COPOLYMERIZATION CATALYSTS CONTAINING CHROME, TITAN AND ANY FLUOR, AND PROCEDURES FOR PREPARING THEREOF. Download PDFInfo
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- NO145680B NO145680B NO773239A NO773239A NO145680B NO 145680 B NO145680 B NO 145680B NO 773239 A NO773239 A NO 773239A NO 773239 A NO773239 A NO 773239A NO 145680 B NO145680 B NO 145680B
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- Prior art keywords
- hydrocarbon
- titanium
- chromium
- catalyst
- oxide
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- 239000003054 catalyst Substances 0.000 title claims description 54
- 238000000034 method Methods 0.000 title claims description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims description 20
- 239000005977 Ethylene Substances 0.000 title claims description 20
- 238000007334 copolymerization reaction Methods 0.000 title claims description 5
- 238000004770 highest occupied molecular orbital Methods 0.000 title 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 150000002430 hydrocarbons Chemical class 0.000 claims description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 24
- 229930195733 hydrocarbon Natural products 0.000 claims description 23
- 239000004215 Carbon black (E152) Substances 0.000 claims description 22
- 239000011651 chromium Substances 0.000 claims description 20
- 239000010936 titanium Substances 0.000 claims description 19
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 18
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 17
- 229910052804 chromium Inorganic materials 0.000 claims description 17
- 229910052719 titanium Inorganic materials 0.000 claims description 16
- -1 chromocene compound Chemical class 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 150000003609 titanium compounds Chemical class 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 claims description 5
- 229910003452 thorium oxide Inorganic materials 0.000 claims description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- TYYBBNOTQFVVKN-UHFFFAOYSA-N chromium(2+);cyclopenta-1,3-diene Chemical compound [Cr+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 TYYBBNOTQFVVKN-UHFFFAOYSA-N 0.000 claims description 4
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 238000004334 fluoridation Methods 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000012025 fluorinating agent Substances 0.000 claims 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 24
- 238000006116 polymerization reaction Methods 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000004913 activation Effects 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 229920000573 polyethylene Polymers 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- WVBBLFIICUWMEM-UHFFFAOYSA-N chromocene Chemical compound [Cr+2].C1=CC=[C-][CH]1.C1=CC=[C-][CH]1 WVBBLFIICUWMEM-UHFFFAOYSA-N 0.000 description 8
- 239000002685 polymerization catalyst Substances 0.000 description 7
- 239000000155 melt Substances 0.000 description 6
- 150000001845 chromium compounds Chemical class 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 150000002222 fluorine compounds Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- LXPCOISGJFXEJE-UHFFFAOYSA-N oxifentorex Chemical compound C=1C=CC=CC=1C[N+](C)([O-])C(C)CC1=CC=CC=C1 LXPCOISGJFXEJE-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- AHXGRMIPHCAXFP-UHFFFAOYSA-L chromyl dichloride Chemical compound Cl[Cr](Cl)(=O)=O AHXGRMIPHCAXFP-UHFFFAOYSA-L 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- CYHOFESITORDDD-UHFFFAOYSA-M C(CCC)O[Cr](=O)(=O)O Chemical group C(CCC)O[Cr](=O)(=O)O CYHOFESITORDDD-UHFFFAOYSA-M 0.000 description 1
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
Foreliggende oppfinnelse angår etylenhomo- og -kopolymeriseringskatalysatorer som inneholder krom og titan og også eventuelt fluor, samt en fremgangsmåte for fremstilling av disse katalysatorer. The present invention relates to ethylene homo- and copolymerization catalysts which contain chromium and titanium and also possibly fluorine, as well as a method for producing these catalysts.
Etylenpolymeriseringskatalysatorer som inneholder krom og titan er kjent. Disse katalysatorer representerer en forbe-dring i forhold til de kjente tidligere katalysatorer som inne-holdt kun krom idet at de ga etylenpolymerer med lavere molekylvekt og som var lettere å behandle enn polyetylenene med høyere molekylvekt. I diverse patenter er det beskrevet spesi-fikke fremgangsmåter for fremstilling av titanmodifiserte krom-katalysatorer for etylenpolymerisering. US patent nr. 3.349.067 beskriver en fremgangsmåte for fremstilling av en polymeriseringskatalysator omfattende å bringe et bærermateriale i kontakt med en oppløsning av en kromholdig forbindelse i et vann-fritt organisk oppløsningsmiddel. I denne beskrivelse angis en reaksjon i nærvær av silisiumoksyd av kromylklorid (Cro2Cl2) og tetra(n-butyl)titanat, noe som gir et bunnfall som inneholder titan og krom, på silisiumoksydbæreren. En slik fremgangsmåte avhenger derfor av reaksjonsproduktet av kromylklorid og det organiske titanat for på en ikke unik måte å avsette seg på substratet. Ethylene polymerization catalysts containing chromium and titanium are known. These catalysts represent an improvement in relation to the known earlier catalysts which contained only chromium in that they gave ethylene polymers with a lower molecular weight and which were easier to process than the polyethylenes with a higher molecular weight. Various patents describe specific methods for producing titanium-modified chromium catalysts for ethylene polymerization. US patent no. 3,349,067 describes a method for producing a polymerization catalyst comprising bringing a support material into contact with a solution of a chromium-containing compound in an anhydrous organic solvent. In this description, a reaction in the presence of silicon oxide of chromyl chloride (Cro 2 Cl 2 ) and tetra(n-butyl) titanate is indicated, which produces a precipitate containing titanium and chromium on the silicon oxide support. Such a method therefore depends on the reaction product of chromyl chloride and the organic titanate to deposit on the substrate in a non-unique way.
US patent nr. 3.622.521 beskriver en katalysator som dannes ved først til en bærer å tilsette en kromholdig forbindelse under anvendelse av et vandig medium og deretter tilset-ning av en titanholdig forbindelse ved bruk av et ikke-vandig medium. En slik fremgangsmåte omfatter anvendelse av to forskjellige oppløsningsmidler og involverer således to separate og adskilte avsetningstrinn. En slik prosess er omstendelig og fører til ikke reproduserbare katalysatorer for etylenpolymerisering. US patent no. 3,622,521 describes a catalyst which is formed by first adding to a support a chromium-containing compound using an aqueous medium and then adding a titanium-containing compound using a non-aqueous medium. Such a method involves the use of two different solvents and thus involves two separate and distinct deposition steps. Such a process is cumbersome and leads to non-reproducible catalysts for ethylene polymerization.
US patent nr. 3.879.362 angår en fremgangsmåte for polymerisering av etylen ved bruk av en katalysator som fremstilles ved (1) å oppvarme en titanforbindelse og et bærermateriale valgt blant silisiumdioksyd, aluminiumoksyd, zirconiumoksyd, toriumoksyd eller blandinger derav, og (2) å oppvarme produktet fra trinn 1 med en kromforbindelse ved en temperatur i området 350-550°C for å oppnå en aktiv katalysator. Et antall kromfor-bindelser er angitt i beskrivelsen inkludert biscyklopentadie-nylkrom, dvs. kromocen. Hovedoppmerksomheten er réttet mot denne totrinnsprosess som involverer enten kromoksyd eller et tertiært butylkromat som kilde for kromforbindelsen. US Patent No. 3,879,362 relates to a process for polymerizing ethylene using a catalyst prepared by (1) heating a titanium compound and a support material selected from silicon dioxide, alumina, zirconium oxide, thorium oxide or mixtures thereof, and (2) to heating the product from step 1 with a chromium compound at a temperature in the range of 350-550°C to obtain an active catalyst. A number of chromium compounds are indicated in the description including biscyclopentadienylchromium, i.e. chromocene. The main focus is on this two-step process involving either chromium oxide or a tertiary butyl chromate as the source of the chromium compound.
Alle de ovenfor angitte fremgangsmåter for fremstilling av disse modifiserte katalysatorer kan.forårsake problemer. Katalysatorene.er følsomme overfor fremstillingsmåtene og kan således gi polyetylener som kan variere i polymeregenskapene med henblikk på molekylvekt, molekylvektsfordeling og densitet. Katalysatoraktiviteten varierer også avhengig av etter hvilken måte katalysatoren er fremstilt. All of the above methods for producing these modified catalysts can cause problems. The catalysts are sensitive to the manufacturing methods and can thus produce polyethylenes that can vary in polymer properties with regard to molecular weight, molecular weight distribution and density. Catalyst activity also varies depending on the way in which the catalyst is produced.
Gjenstand for oppfinnelsen er derfor å frembringe en katalysator for etylenpolymerisering som er enkel å fremstille og som viser tilstrekkelig katalytisk aktivitet. Andre gjen-stander for oppfinnelsen vil fremgå for fagmannen av den føl-gende beskrivelse. The object of the invention is therefore to produce a catalyst for ethylene polymerization which is easy to manufacture and which shows sufficient catalytic activity. Other items for the invention will be apparent to the person skilled in the art from the following description.
Ifølge oppfinnelsen frembringes det således etylenhomo-og -kopolymeriseringskatalysatorer inneholdende krom og titan, eventuelt også fluor, på en bærer som utgjøres av et uorganisk oksyd som According to the invention, ethylene homo- and -copolymerization catalysts containing chromium and titanium, possibly also fluorine, are thus produced on a carrier which consists of an inorganic oxide which
(a) har høyt overflateareal og (a) has high surface area and
(b) er valgt blant aluminiumoksyd, toriumoksyd, silisiumoksyd, zirconiumoksyd og blandinger derav, og (b) is selected from alumina, thorium oxide, silicon oxide, zirconium oxide and mixtures thereof, and
(c) er tørket ved en temperatur på 100-800°C, og (c) is dried at a temperature of 100-800°C, and
denne katalysator karakteriseres ved at den er fremstilt ved følgende trinn: this catalyst is characterized by the fact that it is produced in the following steps:
(1) oppslemming av tørket bærer med et i det vesentlige vann-fritt, flytende hydrokarbon; (2) blanding av oppslemmingen som oppnås i trinn (1) med en oppløsning av en kromocenforbindelse med formel (1) slurrying dried support with a substantially anhydrous liquid hydrocarbon; (2) mixing the slurry obtained in step (1) with a solution of a chromocene compound of formula
hvori hver av Y og Y<1> er en hydrokarbonrest med 1-20 karbonatomer og hver av n og n<1> har en verdi på 0-5, i et flytende hydrokarbon og en titanforbindelse som er oppløselig i hydrokarbon og er kalsinerbar til Ti02, hvorved den resulterende blanding bortsett wherein each of Y and Y<1> is a hydrocarbon residue of 1-20 carbon atoms and each of n and n<1> has a value of 0-5, in a liquid hydrocarbon and a titanium compound which is soluble in hydrocarbon and is calcinable to TiO 2 , whereby the resulting mixture apart
fra hydrokarbon inneholder 0,02 til 3,0 vekt-% elementært krom og 1,0 til 10 vekt-% elementært titan; (3) fjerning av hydrokarbonet for å oppnå en fast rest; (4) oppvarming av produktet fra trinn (3) i en i det vesentlige vannfri oksygenholdig atmosfære ved en temperatur på 30 0 til 1000°C inntil det oppnås en aktiv katalysator. from hydrocarbon containing 0.02 to 3.0 wt% elemental chromium and 1.0 to 10 wt% elemental titanium; (3) removing the hydrocarbon to obtain a solid residue; (4) heating the product from step (3) in a substantially anhydrous oxygen-containing atmosphere at a temperature of 30 0 to 1000°C until an active catalyst is obtained.
Oppfinnelsen angår også en fremgangsmåte for fremstilling av en katalysator av den ovenfor nevnte type og denne fremgangsmåte karakteriseres ved følgende trinn: (1) oppslemming av tørket bærer med et i det vesentlige vann-fritt, flytende hydrokarbon; (2) blanding av oppslemmingen som oppnås i trinn (1) med en oppløsning av en kromocenforbindelse med formel hvori hver av Y og Y<1> er en hydrokarbonrest med 1 til 20 karbonatomer og hver av n og n' har en verdi på 0 til 5 i..et flytende hydrokarbon og en titanforbindelse som er oppløselig i hydrokarbon og er kalsinerbar til TiC^, hvorved den resulterende blanding, eksklusive hydrokarbon, inneholder 0,02 til 3,0 vekt-% elementært krom og 1,0 til 10 vekt-% elementært titan; (3a) fjerning av hydrokarbonet for å oppnå en fast rest; (3b) eventuelt fluoridering med opptil 5 vekt-% av et fluorideringsmiddel, beregnet som F; (4) oppvarming av produktet fra trinn (3) i en i det vesentlige vannfri oksygenholdig atmosfære ved en temperatur av 30 0 til 1000°C inntil det oppnås en aktiv katalysator. The invention also relates to a method for producing a catalyst of the above-mentioned type and this method is characterized by the following steps: (1) slurrying dried carrier with an essentially water-free, liquid hydrocarbon; (2) mixing the slurry obtained in step (1) with a solution of a chromocene compound of formula wherein each of Y and Y<1> is a hydrocarbon residue of 1 to 20 carbon atoms and each of n and n' has a value of 0 to 5 in..a liquid hydrocarbon and a titanium compound which is soluble in hydrocarbon and is calcinable to TiC ^, wherein the resulting mixture, exclusive of hydrocarbon, contains 0.02 to 3.0% by weight elemental chromium and 1.0 to 10% by weight elemental titanium; (3a) removing the hydrocarbon to obtain a solid residue; (3b) optional fluoridation with up to 5% by weight of a fluoridating agent, calculated as F; (4) heating the product from step (3) in a substantially anhydrous oxygen-containing atmosphere at a temperature of 30 0 to 1000°C until an active catalyst is obtained.
I foreliggende beskrivelse har som nevnt kromocenforbin-delsene, også angitt som bis(cyklopentadienyl) krom (II) forbindelser, strukturen: In the present description, as mentioned, the chromocene compounds, also indicated as bis(cyclopentadienyl) chromium (II) compounds, have the structure:
hvori hver av Y og Y' er en hydrokarbonrest med 1 til 20 karbonatomer og hver n og n<1> har en verdi fra 0 til 5. wherein each of Y and Y' is a hydrocarbon residue of 1 to 20 carbon atoms and each n and n<1> has a value from 0 to 5.
Mens blandingen av kromocenforbindelse og bærer i trinn (3) kan inneholde fra "'0,02 til 3 vekt-% krom, er det foretrukket å benytte blandinger som inneholder 0,1 til 1,0 vekt-% krom. While the mixture of chromocene compound and carrier in step (3) may contain from 0.02 to 3% by weight of chromium, it is preferred to use mixtures containing 0.1 to 1.0% by weight of chromium.
Titanforbindelsen som kan benyttes omfatter alle de The titanium compound that can be used includes all of them
som er kalsinerbare til Ti02 under de aktiveringsbetingelser som benyttes, og inkluderer de som er beskrevet i f.eks. US patent nr. 3.622.521. Disse forbindelser inkluderer de som har strukturene which are calcinable to TiO 2 under the activation conditions used, and include those described in e.g. US Patent No. 3,622,521. These compounds include those that have the structures
(I) (R') «Ti(OR') (I) (R') «Ti(OR')
n m n.m
(II) (RO) Ti(OR') „ (II) (RO) Ti(OR') „
m n m n
hvori m er 1, 2, 3 eller 4; n" er 0, 1, 2 eller 3 og m + n" = 4, wherein m is 1, 2, 3 or 4; n" is 0, 1, 2 or 3 and m + n" = 4,
der R er en C1 til C12 alkyl, aryl eller cykloalkyl-gruppe og kombinasjoner derav slik som aralkyl eller alkaryl, where R is a C1 to C12 alkyl, aryl or cycloalkyl group and combinations thereof such as aralkyl or alkaryl,
R' er R, cyklopentadienyl, og C2 til C12 alkenylgrupper slik som etenyl, propenyl, isopropenyl eller butenyl og (III) TiX4 der X, et halogenatom, er fluor, klor, brom eller iod. R' is R, cyclopentadienyl, and C2 to C12 alkenyl groups such as ethenyl, propenyl, isopropenyl or butenyl and (III) TiX4 where X, a halogen atom, is fluorine, chlorine, bromine or iodine.
Titanforbindelsene vil således inkludere titantetra-klorid, tetraisopropyltitanat og tetrabutyltitånat. Titanforbindelsene avsettes hensiktsmessig på bæreren fra en oppløsning i et hydrokarbohoppløsningsmiddel. The titanium compounds will thus include titanium tetrachloride, tetraisopropyl titanate and tetrabutyl titanate. The titanium compounds are conveniently deposited on the support from a solution in a hydrocarbon solvent.
Når det gjelder de organiske titanater er det ingen tydelig gjensidig påvirkning mellom titanforbindelsen og kromocen. Avsetningen av både titan og kromforbindelse er antatt å inntre ved direkte reaksjon med substratet for å gi kjemisk for-ankret titan og krom. En slik vei til de bårede katalysatorer tillater maksimal effektivitet av titan- og kromforbindelsene og tillater meget bedre kontroll med katalysatorfremstillingen enn den fremgangsmåte som er beskrevet i US patent 3.349.067. In the case of the organic titanates, there is no clear mutual influence between the titanium compound and the chromocene. The deposition of both titanium and chromium compound is believed to occur by direct reaction with the substrate to give chemically anchored titanium and chromium. Such a route to the supported catalysts allows maximum efficiency of the titanium and chromium compounds and allows much better control of the catalyst preparation than the method described in US patent 3,349,067.
Titan (som Ti) er tilstede i katalysatoren med henblikk på krom (som Cr), i et molforhold på 0,5 til 180 fortrinnsvis 4 til 35. Titanium (as Ti) is present in the catalyst with respect to chromium (as Cr), in a molar ratio of 0.5 to 180, preferably 4 to 35.
Mens blandingen i trinn (2) kan inneholde fra ca. 1,0 til 10 vekt-% titan, er det foretrukket å fremstille en blanding som inneholder 3 til 7%, beregnet på vekten av den tørkede blanding . While the mixture in step (2) can contain from approx. 1.0 to 10% by weight titanium, it is preferred to prepare a mixture containing 3 to 7%, calculated on the weight of the dried mixture.
Det er ikke nødvendig å inkludere et fluorideringsmiddel. Imidlertid har fluoridering den fordel at det gir en sma-lere molekylvektfordeling og bedre kopolymerisering av a-olefi-ner. Mens opp til 5 vekt-% fluorideringsmiddel kan benyttes, er det foretrukket at det benyttes 0,05 til 1,0%, beregnet som F . It is not necessary to include a fluoridating agent. However, fluoridation has the advantage that it gives a narrower molecular weight distribution and better copolymerization of α-olefins. While up to 5% by weight of fluoridating agent can be used, it is preferred that 0.05 to 1.0% is used, calculated as F .
Fluorideringsforbindelsen som kan benyttes omfatter HF eller en hvilken som helst fluorforbindelse som gir HF under de aktiveringsbetingelser som benyttes. Fluorforbindelser for-skjellig fra HF som kan benyttes er f.eks. ammoniumheksafluor-fosfat, ammoniumheksafluorsilikat, ammoniumtetrafluorborat og ammoniumheksafluortitanat. Fluorforbindelsene blir hensiktsmessig avsatt på bæreren fra en vandig oppløsning derav, eller ved tørrblanding av den faste fluorforbindelse med de andre komponenter av katalysatoren før aktivering. De uorganiske oksydmaterialer som kan benyttes som bærere i katalysatorene ifølge foreliggende oppfinnelse er porøse stoffer med et høyt overflateareal, dvs. et overflateareal som ligger innen området 50 til 1000 m 2 pr. gram, og en partikkelstørrelse- på 50 til 200 ym. De uorganiske oksyder som kan benyttes inkluderer silisiumdioksyd, aluminiumoksyd, toriumoksyd, zirconiumoksyd <p>g blandinger derav. The fluoridating compound which can be used comprises HF or any fluorine compound which gives HF under the activation conditions used. Fluorine compounds other than HF that can be used are e.g. ammonium hexafluorophosphate, ammonium hexafluorosilicate, ammonium tetrafluoroborate and ammonium hexafluorotitanate. The fluorine compounds are suitably deposited on the carrier from an aqueous solution thereof, or by dry mixing of the solid fluorine compound with the other components of the catalyst before activation. The inorganic oxide materials that can be used as carriers in the catalysts according to the present invention are porous substances with a high surface area, i.e. a surface area that lies within the range of 50 to 1000 m 2 per grams, and a particle size of 50 to 200 ym. The inorganic oxides which may be used include silicon dioxide, aluminum oxide, thorium oxide, zirconium oxide and mixtures thereof.
De flytende hydrokarboner kan være alifatiske med 5-10 kaxbonatomer eller aromatiske med 6-10 karbonatomer. Foretrukket er isopentan, heksan, benzen, toluen og xylen. The liquid hydrocarbons can be aliphatic with 5-10 carbon atoms or aromatic with 6-10 carbon atoms. Preferred are isopentane, hexane, benzene, toluene and xylene.
Bæreren bør tørkes før den bringes i kontakt med kromocen- og titanforbindelsene. Dette skjer vanligvis ved enkel oppvarming eller fortørking av katalysatorbæreren med en tørr inert gass .eller tørr luft før bruk. Det er funnet at temperaturen ved tørkingen har en betydelig virkning på molekylvekts-fordelingen og på smelteindeksen for den fremstilte polymer. Den foretrukne tørketemperatur er 100 til 300°C mens temperatu-rer mellom 120 og 250°C er mest foretrukket. Aktivering av katalysatoren kan oppnås ved nær en hvilken som helst temperatur opp til sintringstemperaturen. Føring av en strøm av tørr luft eller oksygen gjennom den bårne katalysator under aktive-ringen understøtter bortdriving av vann fra bæreren. Aktive-ringstemperaturer fra 300 til 9 00°C i korte tidsrom på 6 timer eller deromkring er tilstrekkelig hvis det benyttes godt tørket luft eller oksygen, og temperaturen ikke tillates å stige så langt at det opptrer sintring av bæreren. En foretrukket akti-veringstemperatur er ca. 300 til 800°C. The carrier should be dried before contacting the chromocene and titanium compounds. This usually occurs by simple heating or drying of the catalyst support with a dry inert gas or dry air before use. It has been found that the temperature during drying has a significant effect on the molecular weight distribution and on the melt index of the produced polymer. The preferred drying temperature is 100 to 300°C, while temperatures between 120 and 250°C are most preferred. Activation of the catalyst can be achieved at almost any temperature up to the sintering temperature. Passing a stream of dry air or oxygen through the supported catalyst during activation supports the expulsion of water from the support. Activation temperatures from 300 to 900°C for short periods of 6 hours or thereabouts are sufficient if well-dried air or oxygen is used, and the temperature is not allowed to rise so far that sintering of the support occurs. A preferred activation temperature is approx. 300 to 800°C.
Det kan benyttes bærerkvaliteter med høyt over f lateareal, og mikrosferiode silisiumdioksydpartikler med midlere densitet (MSID) og med et overflateareal på 300 m 2/gram og en porediameter på ca. 200 Å, men midlere partikkelstørrelse på ca. 70 ym, samt silisiumdioksyd med midlere densitet (ID), et overflateareal på ca. 300 m 2/gram, en porediameter på ca. 160 Å og en midlere partikkelstørrelse på ca. 103 ym er foretrukket. Carrier qualities with a high surface area, and microspheroidal silicon dioxide particles with medium density (MSID) and with a surface area of 300 m 2/gram and a pore diameter of approx. 200 Å, but average particle size of approx. 70 ym, as well as silicon dioxide with medium density (ID), a surface area of approx. 300 m 2 /gram, a pore diameter of approx. 160 Å and an average particle size of approx. 103 ym is preferred.
Når det er ønskelig å fremstille etylenpolymerer med høyere smelteindeks, benyttes silisiumoksyder med porevolum på ca. When it is desired to produce ethylene polymers with a higher melting index, silicon oxides with a pore volume of approx.
2,5 cm 3 /g og et overflateareal på ca. 400 m 2/gram. 2.5 cm 3 /g and a surface area of approx. 400 m2/gram.
Oppfinnelsen skal beskrives nærmere i de følgende eksempler der alle deler og prosentangivelser er på vektbasis hvis intet annet er sagt. The invention shall be described in more detail in the following examples where all parts and percentages are by weight unless otherwise stated.
Eksempel 1. Katalysatorfremstilling. Example 1. Catalyst preparation.
Et "G-952-200" microsferoid silisiumdioksyd med midlere densitet, med et overflateareal på ca. 300 m 2/gram og en porediameter på ca. 200 Å ble tørket ved 200°C i 8 timer. Den tør-kede silisiumoksyd (481 g) ble omrørt med tørr isopentan og 5,3 g usubstituert bis(cyklopentadienyl)-krom II (kromocen) og deretter ble 168 g tetraisopropyltitanat tilsatt. Isopentan ble fjernet ved fordampning og man oppnådde en tørr rest bestå-ende av 1,1 vekt-% kromocen og 3 5 vekt-% tetraisopropyltitanat som sammen var avsatt på silisiumdioksydbæreren. Resten ble aktivert ved oppvarming i 2 timer under nitrogen ved 150 oC A "G-952-200" microspheroid silica of medium density, with a surface area of approx. 300 m 2/gram and a pore diameter of approx. 200 Å was dried at 200°C for 8 hours. The dried silica (481 g) was stirred with dry isopentane and 5.3 g of unsubstituted bis(cyclopentadienyl)chromium II (chromocene) and then 168 g of tetraisopropyl titanate was added. Isopentane was removed by evaporation and a dry residue was obtained consisting of 1.1% by weight of chromocene and 35% by weight of tetraisopropyl titanate which were deposited together on the silicon dioxide carrier. The residue was activated by heating for 2 hours under nitrogen at 150 oC
og deretter 2 timer ved 300°C. Nitrogenatmosfæren ble erstattet av luft og oppvarmingen fortsatt ved 300°C i 2 timer. Til slutt ble temperaturen hevet til 800°C og holdt der i 8 timer. Eksempel 2. Katalysatorfremstilling. and then 2 hours at 300°C. The nitrogen atmosphere was replaced by air and the heating continued at 300°C for 2 hours. Finally, the temperature was raised to 800°C and held there for 8 hours. Example 2. Catalyst preparation.
Den fremgangsmåte som er beskrevet i eksempel 1 ble fulgt med følgende forskjeller: (1) Mengden av benyttet silisiumdioksyd var 400 g; (2) mengden av benyttet bis(cyklopentadienyl) krom (II) var 4,4 g; (3) den benyttede mengde av tetraisopropyltitanat var 140 g; og (4) resten ble før aktivering behandlet med 1,2 g ammoniumheksafluorsilikat for å bevirke en avsetning av 0,3 vekt-% på bæreren. The method described in example 1 was followed with the following differences: (1) The amount of silicon dioxide used was 400 g; (2) the amount of bis(cyclopentadienyl) chromium (II) used was 4.4 g; (3) the amount of tetraisopropyl titanate used was 140 g; and (4) the residue, prior to activation, was treated with 1.2 g of ammonium hexafluorosilicate to effect a deposit of 0.3% by weight on the support.
Eksempel 3. Katalysatorbedømmelse. Example 3. Catalyst evaluation.
Katalysatoren som ble fremstilt i eksempel 1 ble bedømt i en hvirvelsjiktreaktor med en diameter på ca. 3 65 mm (til-svarende den som er beskrevet i GB-PS 1.253.063) ved 84°C og et reaktortrykk på 21 kg/cm 2 manometertrykk med en buten/- etylenblanding som var tilstede i et forhold på 0,083. Kata-lysatorproduktiviteten var 5,3 g/(gram Cr x 10~6) . Etylen-buten-kopolymerproduktet hadde en densitet i henhold til ASTM D-1505 på 0,914 g/cm<3> og en smelteindeks i henhold til ASTM D-1238 på 0,87 dg/min. The catalyst prepared in example 1 was evaluated in a fluidized bed reactor with a diameter of approx. 3 65 mm (corresponding to that described in GB-PS 1,253,063) at 84°C and a reactor pressure of 21 kg/cm 2 gauge pressure with a butene/ethylene mixture present in a ratio of 0.083. The catalyst productivity was 5.3 g/(gram Cr x 10~6). The ethylene-butene copolymer product had a density according to ASTM D-1505 of 0.914 g/cm<3> and a melt index according to ASTM D-1238 of 0.87 dg/min.
Eksempel 4. Katalysatorbedømmelse. Example 4. Catalyst evaluation.
Det ble benyttet den samme prosedyre som i eksempel 3 for å bedømme katalysatoren som ble fremstilt i eksempel 2 bortsett fra at buten/etylenforholdet var 0,084. Katalysatorpro-duktiviteten var 4,9 g/(gram Cr x 10~6) . Etylen/butenkopoly-^ meren hadde en densitet på 0,9 20 g/cm 3 og en smelteindeks på 0,17 dg/min. The same procedure as in Example 3 was used to evaluate the catalyst prepared in Example 2 except that the butene/ethylene ratio was 0.084. The catalyst productivity was 4.9 g/(gram Cr x 10~6). The ethylene/butene polymer had a density of 0.9-20 g/cm 3 and a melt index of 0.17 dg/min.
Eksempel 5. Katalysatorfremstilling. Example 5. Catalyst preparation.
Fremgangsmåten som ble beskrevet i eksempel 1 ble modi-fisert ved at 7 ml av en toluenoppløsning inneholdende 0,3 5 g bis(cyklopentadienyl)krom II ble tilsatt til en n-pentan oppslemming av 19,8 g "952" silisiumdioksyd som var tørket ved 200°C, og omrørt under nitrogen i en time hvoretter 6,0 g tetraisopropyltitanat ble tilsatt. Pentan og toluen ble fordampet og resten ble aktivert ved oppvarming i oksygen ved 300°C i 2 timer og ved 720°C i 17 timer. The procedure described in Example 1 was modified in that 7 ml of a toluene solution containing 0.35 g of bis(cyclopentadienyl)chromium II was added to an n-pentane slurry of 19.8 g of "952" silica which had been dried at 200°C, and stirred under nitrogen for one hour after which 6.0 g of tetraisopropyl titanate was added. Pentane and toluene were evaporated and the residue was activated by heating in oxygen at 300°C for 2 hours and at 720°C for 17 hours.
Eksempel 6. Katalysatorfremstilling. Example 6. Catalyst preparation.
18,6 g "952" silisiumdioksyd, tørket ved 200°C ble oppslemmet i n-pentan og 0,34 g bis(cyklopentadienyl)krom II ble tilsatt til oppslemmingen. Etter omrøring i 1 time ble 5,6 g tetraisopropyltitanat tilsatt. n-pentan ble fordampet og resten blandet med 0,19 g ammoniumheksafluorsilikat. Resten ble aktivert ved oppvarming i oksygen i 4 timer ved 3 30°C og 17 timer ved 7 80°C. 18.6 g of "952" silica, dried at 200°C was slurried in n-pentane and 0.34 g of bis(cyclopentadienyl)chromium II was added to the slurry. After stirring for 1 hour, 5.6 g of tetraisopropyl titanate was added. The n-pentane was evaporated and the residue mixed with 0.19 g of ammonium hexafluorosilicate. The residue was activated by heating in oxygen for 4 hours at 3 30°C and 17 hours at 7 80°C.
E ksempel 7. Katalysatorbedømmelse. E xample 7. Catalyst evaluation.
En høytrykksreaksjonsbeholder med røreverk og et reak-torvolum på 1000 ml ble chargert med 0,43 g av katalysatoren som var fremstilt i eksempel 5 og 40 ml 1-hexen. Beholderen A high-pressure reaction vessel with a stirrer and a reactor volume of 1000 ml was charged with 0.43 g of the catalyst prepared in Example 5 and 40 ml of 1-hexene. The container
ble forseglet og satt under trykk med etylen til et trykk på was sealed and pressurized with ethylene to a pressure of
14 kg/cm 2 manometertrykk. Polymeriseringen ble foretatt ved 86°C i 12 minutter. Det ble oppnådd et utbytte på 78 gram etylenpolymer ved en smelteindeks på 147 dg/min. og en densitet på 0,9 22 g/cm<3>. 14 kg/cm 2 manometer pressure. The polymerization was carried out at 86°C for 12 minutes. A yield of 78 grams of ethylene polymer was obtained at a melt index of 147 dg/min. and a density of 0.9 22 g/cm<3>.
I et andre forsøk som skilte seg fra det ovenfor be-skrevne kun i det at det ble benyttet 0,31 g katalysator, og i det at polymeriseringstiden var 15 minutter, ble det oppnådd et etylenpolymerutbytte på 86 gram med en smelteindeks på 166 dg/min. og en densitet på 0,917 g/cm 3. In a second experiment which differed from the one described above only in that 0.31 g of catalyst was used, and in that the polymerization time was 15 minutes, an ethylene polymer yield of 86 grams was obtained with a melt index of 166 dg/ my. and a density of 0.917 g/cm 3.
Eksempel 8. Katalysatorbedømmelse. Example 8. Catalyst evaluation.
Eksempel 7 ble gjentatt to ganger ved bruk av 0,3 5 g henholdsvis 0,3 2 gram katalysator fremstilt ifølge eksempel 6 og med .polymeriseringstider på 30 hhv. 20 minutter. Det ble oppnådd etylenpolymerer i utbytter på 120 hhv. 56 gram. Smelte-indeksene var 0,32 dg/min. hhv. 0,64 dg/min. og densiteten var 0,918 g/cm<3> hhv. 0,917 g/cm<3>. Example 7 was repeated twice using 0.35 g and 0.32 g of catalyst prepared according to example 6 and with polymerization times of 30 and 30, respectively. 20 minutes. Ethylene polymers were obtained in yields of 120 or 56 grams. The melting indices were 0.32 dg/min. respectively 0.64 dg/min. and the density was 0.918 g/cm<3> respectively. 0.917 g/cm<3>.
Katalysatorene ifølge oppfinnelsen ble også sammenlignet med katalysatorer ifølge US patent nr. 3.879.362. The catalysts according to the invention were also compared with catalysts according to US patent no. 3,879,362.
Kontroll A: Polymerisering av etylen ved bruk av kjent katalysator . Control A: Polymerization of ethylene using a known catalyst.
Det ble fremstilt en etylenpolymeriseringskatalysator ved den teknikk som er beskrevet i US patent nr. 3.879.362 som følger. An ethylene polymerization catalyst was prepared by the technique described in US Patent No. 3,879,362 as follows.
En andel av "952" silisiumdioksydbærer ble tørket ved 200°C. Deretter ble 14,9 gram av den tørkede silisiumdioksyd oppslemmet i tørr pentan og blandet med 4,5 gram tetraisopropyltitanat. Pentan ble fjernet ved fordamping og resten aktivert ved 780°C i 16 timer i en oksygenstrøm. En oppslemming av 15,6 gram av denne aktiverte rest ble preparert i pentan hvortil det ble tilsatt 0,27 gram kromocen. Pentan ble fjernet ved fordamping, resten kort oppvarmet under nitrogen for å fjerne de siste pentanspor og resten deretter aktivert ved 810°C i 16 timer i en oksygenstrøm. Den aktiverte rest ble benyttet som polymeriseringskatalysator for å polymerisere etylen i en omrørt auto-klav ved bruk av heksan som fortynningsmiddel. Det ble benyttet en polymeriseringstemperatur på 90°C ved et totalt trykk på 14 kg/cm 2 manometertrykk i 1 time. Lignende forsøk ga polyetylener med flytindekser på 2,8 hhv. 2,4, målt i henhold til ASTM 1238 ved 10 ganger den vekt som ble benyttet for smelteindeksbestem-melsene ved 190°C. A portion of "952" silica support was dried at 200°C. Then 14.9 grams of the dried silica was slurried in dry pentane and mixed with 4.5 grams of tetraisopropyl titanate. Pentane was removed by evaporation and the residue activated at 780°C for 16 hours in an oxygen stream. A slurry of 15.6 grams of this activated residue was prepared in pentane to which 0.27 grams of chromocene was added. Pentane was removed by evaporation, the residue briefly heated under nitrogen to remove the last traces of pentane and the residue then activated at 810°C for 16 hours in an oxygen stream. The activated residue was used as a polymerization catalyst to polymerize ethylene in a stirred autoclave using hexane as diluent. A polymerization temperature of 90°C was used at a total pressure of 14 kg/cm 2 manometer pressure for 1 hour. Similar experiments yielded polyethylenes with flow indices of 2.8 and 2.4, measured according to ASTM 1238 at 10 times the weight used for the melt index determinations at 190°C.
Eksempel 9. : Polymerisering av etylen ved bruk av katalysatoren ifølge oppfinnelsen. Example 9: Polymerization of ethylene using the catalyst according to the invention.
Det ble fremstilt en etylenpolymeriseringskatalysator som følger. An ethylene polymerization catalyst was prepared as follows.
En oppslemming av 15,2 gram "952" silisiumdioksyd som var tørket ved 200°C ble preparert i pentan. Oppslemmingen ble blandet med 0,26 gram kromocen. Umiddelbart deretter ble 4,6 gram tetraisopropyltitanat blandet inn i oppsiemmingen. Pentan ble fjernet ved fordamping. Etter en kort oppvarming under nitrogen for å fjerne spor av pentan ble resten aktivert i en oksy-genstrøm ved 780°C i 16 timer. Denne aktiverte rest ble benyttet som polymeriseringskatalysator ved bruk av den samme prosedyre <p>g det samme utstyr som i kontroll A for å polymerisere etylen, igjen ved bruk av heksan som fortynningsmiddel. Det ble benyttet en polymeriseringstemperatur på 9 0°C under et totalt trykk på 14 kg/cm 2 manometertrykk i 1 time. Det ble gjennomført 3 polymeriseringer som ga polyetylener med flytindekser på 11,9, 4,8 og 3,6. A slurry of 15.2 grams of "952" silica which had been dried at 200°C was prepared in pentane. The slurry was mixed with 0.26 grams of chromocene. Immediately thereafter, 4.6 grams of tetraisopropyl titanate were mixed into the sieving. Pentane was removed by evaporation. After a brief heating under nitrogen to remove traces of pentane, the residue was activated in an oxygen stream at 780°C for 16 hours. This activated residue was used as a polymerization catalyst using the same procedure <p>g the same equipment as in control A to polymerize ethylene, again using hexane as diluent. A polymerization temperature of 90°C was used under a total pressure of 14 kg/cm 2 gauge pressure for 1 hour. 3 polymerizations were carried out which gave polyethylenes with flow indices of 11.9, 4.8 and 3.6.
De ovenfor gitte eksperimentelle data viser at når det er variasjoner i flytindeksen innen en serie replikatpolymeri-seringer gir katalysatoren ifølge foreliggende oppfinnelse betydelig høyere flytindekser enn de som fremstilles ifølge den kjente teknikk, noe som skyldes forskjeller i tilsetningrekke-følgen for katalysatorkomponentene og også varmeaktiverings-trinnene, begge deler ting som gir forskjellige etylenpolymeriseringskatalysatorer. The experimental data given above show that when there are variations in the flow index within a series of replicate polymerizations, the catalyst according to the present invention gives significantly higher flow indices than those produced according to the known technique, which is due to differences in the order of addition of the catalyst components and also heat activation steps, both sharing things that provide different ethylene polymerization catalysts.
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US4803253A (en) * | 1982-03-30 | 1989-02-07 | Phillips Petroleum Company | Ethylene polymer produced using a catalyst comprising a phosphate and with a bis-(cyclopentadienyl)chromium(II) compound |
US4424139A (en) | 1982-03-30 | 1984-01-03 | Phillips Petroleum Company | Catalyst comprising a phosphate and with a bis-(cyclopentadienyl)chromium(II) compound |
US4690990A (en) * | 1982-03-30 | 1987-09-01 | Phillips Petroleum Company | Polymerization process using a catalyst comprising a phosphate and with a bis-(cyclopentadienyl)chromium(II) compound |
US4522987A (en) * | 1982-07-09 | 1985-06-11 | Phillips Petroleum Company | Low density polyethylene |
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1976
- 1976-09-22 US US05/725,542 patent/US4101445A/en not_active Expired - Lifetime
-
1977
- 1977-08-29 ZA ZA00775232A patent/ZA775232B/en unknown
- 1977-09-02 CA CA286,021A patent/CA1098106A/en not_active Expired
- 1977-09-19 AU AU28909/77A patent/AU519542B2/en not_active Expired
- 1977-09-20 PH PH20255A patent/PH13455A/en unknown
- 1977-09-21 EG EG540/77A patent/EG13094A/en active
- 1977-09-21 NL NLAANVRAGE7710349,A patent/NL174723C/en not_active IP Right Cessation
- 1977-09-21 NO NO773239A patent/NO145680C/en unknown
- 1977-09-21 AR AR269282A patent/AR222295A1/en active
- 1977-09-21 GB GB39409/77A patent/GB1574877A/en not_active Expired
- 1977-09-21 IT IT27819/77A patent/IT1085044B/en active
- 1977-09-21 CS CS805762A patent/CS221952B2/en unknown
- 1977-09-21 SE SE7710593A patent/SE438314B/en not_active IP Right Cessation
- 1977-09-21 NZ NZ185222A patent/NZ185222A/en unknown
- 1977-09-21 FR FR7728407A patent/FR2365590A1/en active Granted
- 1977-09-21 DK DK417277A patent/DK149205C/en not_active IP Right Cessation
- 1977-09-21 MX MX776202U patent/MX4472E/en unknown
- 1977-09-21 DE DE2742543A patent/DE2742543C2/en not_active Expired
- 1977-09-21 JP JP11274877A patent/JPS5339992A/en active Granted
- 1977-09-21 ES ES462508A patent/ES462508A1/en not_active Expired
- 1977-09-21 CS CS776117A patent/CS221951B2/en unknown
- 1977-09-21 BE BE181083A patent/BE858910A/en not_active IP Right Cessation
- 1977-09-21 FI FI772791A patent/FI63246C/en not_active IP Right Cessation
- 1977-09-21 BR BR7706288A patent/BR7706288A/en unknown
- 1977-09-22 IN IN1430/CAL/77A patent/IN147225B/en unknown
- 1977-09-22 RO RO7791632A patent/RO73241A/en unknown
- 1977-11-24 ES ES464417A patent/ES464417A1/en not_active Expired
-
1980
- 1980-03-24 NO NO800836A patent/NO153611C/en unknown
-
1981
- 1981-08-06 HK HK389/81A patent/HK38981A/en unknown
-
1982
- 1982-12-30 MY MY80/82A patent/MY8200080A/en unknown
-
1983
- 1983-01-26 SE SE8300395A patent/SE445460B/en not_active IP Right Cessation
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